Zirconium (Zr) alloys are widely used in nuclear energy because of their excellent mechanical properties and low thermal neutron absorption cross-section. This work investigated the printability, microstructure, and mechanical properties of Zr-4 alloy additively manufactured by laser powder bed fusion (LPBF) for the first time. The effect of annealing temperature on the microstructural and the mechanical property evolution of the printed Zr-4 alloy was studied. The results exhibited that the Zr-4 alloy with a high relative density of 99.77% was obtained using optimised printing parameters. With an increase in the annealing temperature, the formed α phase of the Zr-4 alloy changed from an acicular shape to a coarse-twisted shape, and finally to an equiaxed shape. Such microstructure change endowed the alloy with a high compressive strength of 2130 MPa and compressive strain of 36%. When the annealing temperature exceeded 700°C, Zrx(Fe2Cr) compounds were precipitated, strengthening the alloy by pinning effect. These findings provide valuable guidance for the manufacture of geometrically complex Zr alloy parts for nuclear power applications.